Biohybrid microcapsules based on electrosprayed CS-immobilized nanoZrV for self-healing epoxy coating development.

In this work, zirconium vanadate nanoparticles were immobilized into chitosan using a facile electrospraying technique to produce CS-ZrV hybrid microcapsules for the development of a self-healing coating. Upon assessment, hybrid microcapsules possessed desirable properties with a mean particle size of 319 µm, maintaining good thermal stability of ∼55% at 700 °C, and were subsequently incorporated into an epoxy resin to develop a biocompatible self-healing coating, CZVEx, for carbon steel corrosion protection. Scratched samples of self-healing and control coatings were analyzed in a corrosion medium of 3.5 wt% aqueous NaCl. SEM images of the scratched coating sample, after days of immersion, revealed healing of defects through the appearance of an epoxide gel-like substance due to the release of polymeric vanadate that reacted with corrosion agents, resulting in polymerization of vanadium hydrates and subsequent self-healing, validated by the proposed mechanism of self-healing. Electrochemical impedance spectroscopy analysis further confirmed CZVEx coating possessed excellent self-healing capabilities through a significant impedance rise from 4.48 × 105 to 5.52 × 105 (ohm cm2) between the 7th and 14th day of immersion. Furthermore, comparative polarization assessment of coating samples with/without defects indicated the accuracy of EIS for self-healing analysis, and showed the sample with no defect was only 2.6 times more corrosion resistant than the scratched coating, as against bare steel substrate that was 22 times less resistant, revealing superior self-healing anticorrosion properties of the coating.

Electrospraying of Bio-Based Chitosan Microcapsules Using Novel Mixed Cross-Linker: Experimental and Response Surface Methodology Optimization.

Chitosan microcapsules draw attention due to their biodegradability, biocompatibility, antibacterial behavior, low cost, easy processing, and the capability to be used for different applications. This study utilized the electrospraying technique for the chitosan microcapsules formulation. As a novel cross-linking agent, a mixture of oxalic acid and sodium phosphate dibasic was utilized as a collecting solution for the first time in the electrospraying of chitosan microcapsules. Scanning Electron Microscopy (SEM) was utilized to optimize the spherical morphology and size of the experimentally obtained microcapsules. The different parameters, including chitosan concentration, applied voltage, flow rate, and tip-to-collector (TTC) distance, affecting the microcapsules' size, sphericity, yield, and combined effects were optimized using Surface Responses Methodology (RSM). The Analysis of Variance (ANOVA) was utilized to obtain the impact of each parameter on the process responses. Accordingly, the results illustrated the significant impact of the voltage parameter, with the highest F-values and least p-values, on the capsule size, sphericity, and yield. The predicted optimum conditions were determined as 5 wt% chitosan concentration, 7 mL/h flow rate, 22 kV, and 8 cm TTC distance. The predicted responses at the optimized conditions are 389 µm, 0.72, and 80.6% for the capsule size, sphericity, and yield, respectively. While the validation of the model prediction was conducted experimentally, the obtained results were 369.2 ± 23.5 µm, 0.75 ± 0.04, and 87.3 ± 11.4%, respectively. The optimization process was successfully examined for the chitosan microcapsules manufacturing.